CN114426549A - Method for preparing dicyclopentadiene dioxide DCPDO and 2-phenyl-2-propanol - Google Patents

Method for preparing dicyclopentadiene dioxide DCPDO and 2-phenyl-2-propanol Download PDF

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CN114426549A
CN114426549A CN202011103987.1A CN202011103987A CN114426549A CN 114426549 A CN114426549 A CN 114426549A CN 202011103987 A CN202011103987 A CN 202011103987A CN 114426549 A CN114426549 A CN 114426549A
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CN114426549B (en
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翁羽飞
孙荣华
范存良
周飞
奚军
蒋方红
许艾娜
曹强
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China Petroleum and Chemical Corp
Sinopec Shanghai Petrochemical Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The invention discloses a method for preparing dicyclopentadiene dioxide DCPDO and 2-phenyl-2-propanol, which comprises the following steps: reacting DCPD with CHP in the presence of inert solvent to generate dicyclopentadiene dioxide and 2-phenyl-2-propanol by taking a titanium-silicon molecular sieve as a catalyst; then a double-tower series rectification separation process is adopted, the solvent and the 2-phenyl-2-propanol are collected at the tops of the first rectifying tower and the second rectifying tower, and the DCPDDO is collected at the bottom of the second rectifying tower; and (3) crystallizing and separating the DCPDO collected from the tower kettle to obtain solid DCPDO, mixing unreacted raw materials or dicyclopentadiene monooxide in crystallization mother liquor with fresh reaction raw materials again, and feeding the mixture into a reactor for continuous reaction. The preparation process can reuse unreacted raw materials or the dicyclopentadiene monooxide, has high product yield, obviously reduces the discharge amount of waste liquid, has safe process operation and provides a green reaction process for synthesizing the DCPDO.

Description

Method for preparing dicyclopentadiene dioxide DCPDO and 2-phenyl-2-propanol
Technical Field
The invention belongs to the technical field of catalytic oxidation synthesis of organic epoxy compounds and catalytic oxidation of olefins, and particularly relates to preparation and separation of (3, 4), (8, 9) -diepoxy-tricyclo [5,2,1,0 ] by taking dicyclopentadiene as a raw material and a titanium silicalite molecular sieve as a catalyst2,6]Decane (commonly known as dicyclopentadiene dioxide, DCPDDO), 2-phenyl-2-propanol.
Background
Dicyclopentadiene (DCPD), scientific name: tricyclic [5,2,1,0 ] s2,6]Decadiene-3, 8, which is an important component in the carbon five fraction of petroleum cracking, accounts for about 14 to 19 percent of the carbon five fraction. Dicyclopentadiene Dioxide (DCPDDO), a product of epoxidation of dicyclopentadiene, with the scientific names (3, 4), (8, 9) -diepoxy-tricyclo [5,2,1,02,6]Decane, a cycloaliphatic epoxide with excellent properties. Compared with common epoxy resin, the dicyclopentadiene dioxide has better performances in the aspects of high temperature resistance, heat resistance, weather resistance, ultraviolet resistance, electric insulation, high strength and the like. Based on the properties, the dicyclopentadiene dioxide is widely used for high-temperature resistant casting materials, glass fiber reinforced plastics, adhesives and laminated materialsAnd electronic device packaging.
In the prior art, dicyclopentadiene dioxide is usually prepared from dicyclopentadiene through epoxidation reaction by methods such as an acetic acid peroxide method, a chlorohydrin method, a hydrogenated peroxide catalytic epoxidation method and the like, but the three methods all have the defects at present, such as complex reaction process, serious equipment corrosion, easy generation of by-products of acidic ring opening of epoxide, high discharge of three wastes and the like. In recent years, a green epoxidation process using hydrogen peroxide as an oxygen source and a heteropoly acid compound as a catalyst has attracted much attention. The catalyst can be divided into a homogeneous catalyst and a heterogeneous catalyst according to a catalytic action mechanism, the homogeneous catalysis reaction is to directly add heteropoly acid or salts thereof into a reaction system, the catalysis efficiency is high, but the catalyst is not easy to recover, the cost is high, and the three wastes are more; the heterogeneous catalytic reaction realizes the recycling of the catalyst while keeping relatively high catalytic efficiency, thereby obtaining extensive attention and intensive research of domestic and foreign researchers. Venturillo et al reported Na2WO4/H3PO4/H2O2In the presence of phase transfer catalyst, the conversion rate of reaction to most of olefin such as cyclohexene and styrene is 95%, and the selectivity of epoxy compound is about 80% (J.Org.chem,1983,48(21): 3831-3833). Ishii et al reported heteropolyacid H3PW12O40Or H3PMo12O40With cetylpyridinium chloride in the presence of a catalyst consisting of 35% H2O2Epoxidation of a variety of organic substrates can be carried out efficiently in either homogeneous or two-phase systems. However, when the catalyst system is used for synthesizing dicyclopentadiene dioxide, the disadvantages of easy loss of heteropoly acid, high difficulty in separating and recovering the catalyst, less times of repeated use and the like exist, and the catalyst system is difficult to be used in industrial devices (J.org.chem,1998, 53 (15): 3587-3593). Li et al reported that H3PW12O40Impregnating the silica surface with H2O2Is used as oxidant for synthesizing dicyclopentadiene dioxide, has high initial activity, but is adsorbed in the reaction processThe heteropoly acid on the surface of the silicon dioxide is easy to run off, and the catalyst can not be reused (green new synthesis process for preparing dicyclopentadiene dioxide by catalyzing dicyclopentadiene with heteropoly acid [ D)]Jilin, university of northeast teachers, 2007). Therefore, the heteropoly acid is loaded on the surface of the silicon dioxide by an immersion method and a sol-gel method, although the problem of catalyst recovery can be solved, the heteropoly acid is easy to fall off from the surface of a catalyst carrier in the reaction process, so that the service life of the catalyst is short, the activity of the catalyst is obviously reduced after the heteropoly acid is generally repeatedly used for 5-6 times, and the heteropoly acid is not easy to be used in an industrial generation device. In conclusion, in the heterogeneous catalytic oxidation method for preparing the epoxypentadiene dioxide, although the catalyst is recycled, the problem that the heteropoly acid is easy to fall off to cause short service life of the catalyst exists.
Because of the presence of two double bonds in the DCPD molecule, excess organic peroxide is required for complete conversion of DCPD to dicyclopentadiene dioxide. The excessive organic peroxide brings many problems to the separation and purification of the product and also brings many adverse effects to the activity of the catalyst. If the peroxide is not excessive, part of DCPD undergoes epoxidation reaction only with one double bond to generate dicyclopentadiene monooxide which has two structures with the scientific names of 3, 4-epoxy-tricyclo [5,2,1,0 ]2,6]Decene-8, or 8, 9-epoxy-tricyclo [5,2,1,0 ]2,6]Decene-3, a chemical intermediate, has important application prospects in the fields of fine chemical engineering and epoxy resin.
Disclosure of Invention
In order to solve the defects of the synthesis process of dicyclopentadiene dioxide, the inventor finds that dicyclopentadiene dioxide (DCPDO) can be effectively synthesized by using titanium silicalite molecular sieve catalyst and organic peroxide as an oxidant, and the reaction yield can reach 95-100%. The existing Ti-HMS molecular sieve catalyst is used for synthesizing DCPDO, has good initial activity, but the reaction activity is obviously reduced along with the increase of the using times. The important reason is that the excessive organic peroxide can introduce more water into a reaction system, the organic peroxide is partially decomposed in the reaction process to generate water and acid, the self polymerization of reaction products is easily caused, the pore channels of the catalyst are blocked, the HMS framework is broken, titanium is lost, and the catalyst is deactivated, so that the application of Ti-HMS in the synthesis of dicyclopentadiene dioxide is limited.
In order to solve the problem, firstly, the invention improves the titanium-containing molecular sieve catalyst Ti-HMS with mesoporous characteristic, and magnesium oxide and nano carbon fiber are introduced into the catalyst, so that the waterproof and anti-coking performances of the Ti-HMS are greatly improved. Thirdly, the proportion of the raw materials is controlled to ensure that the conversion rate of DCPD and organic peroxide in the reaction product is more than 99 percent in the reactor, and the dicyclopentadiene dioxide is separated by utilizing the rectification and crystallization separation technology. The dicyclopentadiene monooxide or unreacted CHP in the product is recycled to the reactor again, and is mixed with fresh reaction raw materials for continuous reaction, thereby effectively solving the problems of product separation and purification and the like caused by excessive organic peroxide in the reaction product.
The technical scheme of the invention is specifically introduced as follows.
The invention provides a method for preparing dicyclopentadiene dioxide DCPDDO and 2-phenyl-2-propanol, which comprises the following steps:
(1) firstly, dicyclopentadiene DCPD is taken as a reaction raw material, cumene hydroperoxide CHP is taken as an oxidant, and the DCPD, the CHP and a titanium silicalite molecular sieve catalyst are fully contacted in an inert solvent to carry out catalytic oxidation reaction to generate main products (3, 4), (8, 9) -diepoxy-tricyclo [5,2,1,02,6]A mixture of decane DCPDO and 2-phenyl-2-propanol;
the titanium silicalite molecular sieve catalyst is a modified Ti-HMS molecular sieve catalyst with mesoporous characteristics, and comprises the following components: TiO 220.10-6.15 percent of mass fraction, 45.15-66.59 percent of mass fraction of nano carbon fiber and SiO2The mass fraction is 26.60-45.80%, the mass fraction of magnesium oxide is 0.01-2.00%, the silane group is 0.40-6.90%, and the UV-vis spectrogram of the catalyst has a strong absorption peak at 220 nm;
the catalytic oxidation reaction temperature is 30-150 ℃, the pressure is 0-10 MPa (gauge pressure), the mole ratio of CHP to DCPD is preferably 1.8: 1-2.5: 1, the volume ratio of inert solvent to DCPD is preferably 5: 1-30: 1;
(2) carrying out double-tower continuous rectification separation on the mixed liquor obtained in the step (1), returning 50-80% of the inert solvent collected at the top of the first rectification tower to a feed inlet of a catalytic oxidation reactor for recycling in the reactor, taking the rest 20-50% of the solvent as a DCPDO crystallization separation solvent, and conveying the tower bottom liquid to a second rectification tower; 2-phenyl-2-propanol is collected at the top of the second rectifying tower, dicyclopentadiene dioxide, dicyclopentadiene mono-oxide and unreacted raw materials are collected at the bottom of the second rectifying tower;
the first rectifying tower adopts reduced pressure rectification, the operating pressure of the tower top is 300-3000 Pa, the reflux ratio is 2: 1-10: 1, the temperature of the top of the tower is 20-60 ℃, the temperature of a tower kettle is 70-130 ℃, a solvent is collected at the top of the tower, and materials in the tower kettle are sent to a second rectifying tower;
and the second rectifying tower adopts reduced pressure rectification, the operating pressure at the top of the tower is 100-3000 Pa, and the reflux ratio is 2: 1-10: 1, the temperature of the top of the tower is 40-100 ℃, the temperature of a tower kettle is 60-155 ℃, the fraction collected at the top of the tower is 2-phenyl-2-propanol, and dicyclopentadiene dioxide, dicyclopentadiene monooxide and unreacted raw materials are collected at the tower kettle;
(3) adding an organic solvent into the DCPDO material collected in the tower kettle of the second rectifying tower in the step (2), and preparing a DCPDO saturated solution at the normal pressure and the temperature of 60-100 ℃, wherein the mass ratio of the DCPDO to the organic solvent is 1: 2-1: and 20, cooling the saturated solution to-5-30 ℃, precipitating DCPDO solid in the solution, and separating to obtain solid DCPDO and crystallization mother liquor (the dicyclopentadiene monooxide and the unreacted CHP are enriched in the crystallization mother liquor).
Further, the catalytic oxidation reaction temperature in the step (1) is 60-140 ℃, the pressure is 0.3-3 MPa (gauge pressure), and the molar ratio of CHP to DCPD is 1.8: 1-2.2: 1.
Further, the catalytic oxidation reaction in the step (1) adopts a batch reaction process or a fixed bed continuous reaction process; adopting an intermittent reaction process, wherein the mass ratio of the catalyst consumption to the DCPD is 0.01: 100-20: 100, the reaction time is 1-20 hours; a fixed bed continuous reaction process is adopted, and the total material volume airspeed is 0.1-4.2 h-1。
Further, the mass ratio of the catalyst to the DCPD in the step (1) is 0.5: 100-15: 100, and the reaction time is 2-6 hours.
Further, the inert solvent in the step (1) is selected from any one of hexane, heptane, octane, nonane, decane, undecane, benzene, toluene, ethylbenzene, methylethylbenzene, xylene, cumene and petroleum ether.
Further, in the step (2), the first rectifying tower is subjected to reduced pressure rectification, the operating pressure at the top of the tower is 600-2000 Pa, the reflux ratio is 5: 1-8: 1, the temperature at the top of the tower is 25-46 ℃, and the temperature at the bottom of the tower is 80-125 ℃.
Further, in the step (2), the second rectifying tower adopts reduced pressure rectification, the operating pressure at the top of the tower is 300-2000 Pa, and the reflux ratio is 5: 1-8: 1, the temperature of the top of the tower is 60-95 ℃, and the temperature of the bottom of the tower is 90-145 ℃.
Further, the mass ratio of DCPDDO to the organic solvent in the step (3) is 1: 4-1: and 20, cooling the saturated solution to 20-30 ℃.
Further, the organic solvent in the step (3) is any one of hexane, heptane, octane, nonane, decane, undecane, benzene, toluene, ethylbenzene, methylethylbenzene, xylene, cumene and petroleum ether.
The above-mentioned method for preparing (3, 4), (8, 9) -diepoxy-tricyclo [5,2,1,02,6] decane further comprises the step (4), specifically as follows:
(4) returning the crystallization mother liquor obtained in the step (3) to the catalytic oxidation reactor in the step (1), mixing with reaction raw materials DCPD, CHP and an inert solvent, and continuously reacting; or conveying the crystallized mother liquor to the first rectifying tower in the step (2) for rectifying and separating the solvent in the crystallized mother liquor.
Since the excess organic peroxide not only affects the catalyst reactivity, it is also difficult to separate it from the reaction product. If not, the product is subjected to post-treatment to cause safety problems, the product quality index is influenced, and the consumption of organic peroxide is increased. The present invention provides a method for effectively solving the problem, which comprises the following steps: the molar ratio of DCPD to cumene hydroperoxide is preferably controlled to be 1: 1.8-1: within the range of 2.2, DCPD reacts with cumyl peroxide to generate dicyclopentadiene dioxide, the inert solvent and 2-phenyl-2-propanol are separated by rectification under reduced pressure, dicyclopentadiene dioxide is separated by crystallization, the monocyclopentadiene oxide solution, DCPD and unreacted cumyl hydroperoxide in the crystallization mother liquor are mixed with fresh reaction raw materials DCPD and CHP and enter an oxidation reactor for continuous reaction, the conversion rate of DCPD and CHP is kept between 99 percent and 100 percent, and the DCPD and CHP in the reaction materials are fully utilized.
The preparation method of the titanium silicalite molecular sieve catalyst comprises the following steps:
a) dissolving a silicon source, a titanium source and a template agent in a mixed solvent of water and organic alcohol under an inert atmosphere, stirring and crystallizing for 0.5-10 hours at room temperature, adding the nano carbon fiber, continuously stirring for 10-72 hours, then crystallizing for 1-7 days at 150-200 ℃, and separating, washing and drying a crystallized product to obtain the nano carbon fiber-loaded Ti-HMS;
b) putting the Ti-HMS loaded by the nano carbon fiber into a container containing Mg (OH)2、MgO、MgCO3、4MgCO3。Mg(OH)25H2O, dolomite (MgCO)3.CaCO3) Stirring the mixture of any one or more of the above in an aqueous solution at room temperature for 10-48 hours, separating out solids, washing the obtained solution with water until the solution is neutral, drying the solution, and roasting the solution at 300-1000 ℃ for 2-20 hours in an inert atmosphere to obtain a Ti-HMS catalyst matrix modified by a magnesium-containing compound and taking carbon nanofibers as a carrier;
c) treating the Ti-HMS catalyst matrix with an organic silicon solution at the temperature of 25-300 ℃ for 0.5-100 hours; the dosage of the organic silicon is 10 to 70 percent of the weight of the Ti-HMS catalyst matrix; and then filtering and separating out the solid catalyst, washing the solid catalyst by using an inert solvent, and baking the solid catalyst for 10-24 hours in an environment with the pressure of 0.133-1.33 KPa and the temperature of 80-200 ℃ to prepare the magnesium-containing compound modified Ti-HMS/nano carbon fiber composite catalyst.
Further, in the step a), the silicon source is one or two of orthosilicate ester or alkyl silicate ester; the titanium source is titanate; the template agent is organic amine with a general formula of RNH2, and R is a chain alkyl with 6-18 carbon atoms; the molar ratio of RNH2 to Si in the silicon source is 0.01-0.3: 1, and the molar ratio of Si in the silicon source to Ti in the titanium source is 5: 1-500: 1, the molar ratio of water to a silicon source is 4-20: 1, the volume ratio of alcohol to the silicon source is 1-4: 1, and the molar ratio of carbon nanofibers to the silicon source is 5-20: 1.
Further, the titanate used is selected from any one of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate and tetraisobutyl titanate.
Further, in step a), the nano carbon fiber used is prepared from a carbon-containing gas source, preferably CO and CH4、C2H6、C3H8Any one of the carbon nano-fibers is used as a reaction raw material, a single metal element or a multi-element alloy of any one of elements in the VIII group of the periodic table, more preferably Fe, Co and Ni is used as a catalyst, and the carbon nano-fibers are formed by catalytic cracking reaction of a carbon-containing gas source, wherein the catalytic growth temperature of the carbon nano-fibers is 550-650 ℃.
Further, in the step b), the volume ratio of the nano carbon fiber-supported Ti-HMS to the magnesium-containing compound aqueous solution is 1: 1-1: 3, MgO, Mg (OH)2、MgCO3、4MgCO3。Mg(OH)2·5H2The molar ratio of any one or a mixture of more of O and dolomite to the silicon source used in the step a) is 0.01: 100-7: 100, respectively; the roasting temperature is 400-800 ℃, and the roasting time is 3-8 hours.
Further, in step c), the organosilicon solution is selected from any one of halosilane, silazane or silylamine.
Further, in step c), the organosilicon is selected from any one of trimethylchlorosilane, triethylsilicon chloride, hexamethyldisilazane or N-trimethylsilylimidazole.
Further, in the step c), the organic silicon solution and the solvent are selected from any one or a mixture of benzene, toluene, isopropyl benzene, ethylbenzene, cyclohexane, n-heptane, octane and dodecane.
Further, in step c), washing with an inert solvent comprises: and (3) washing the solid catalyst for 3 times by using toluene, benzene or alkane inert solvent, wherein the volume of the inert solvent used for washing each time is 5-10 times that of the solid catalyst.
Compared with the prior art, the invention has the following advantages:
the preparation method provided by the invention is used for synthesizing dicyclopentadiene dioxide, has the advantages of good catalyst activity, long service life and high product yield, fully utilizes DCPD and CHP in reaction materials, effectively solves the problem of product separation caused by excessive CHP, is simple and convenient in process control, and greatly improves the safety of the reaction process. By using the crystallization separation technology, the problems of separation and purification of DCPDO and dicyclopentadiene monooxide are solved, unreacted dicyclopentadiene monooxide or CHP can be recycled, and the product yield is higher.
Drawings
FIG. 1 is a process flow diagram of the preparation method of the present invention.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention is further illustrated by the following examples, but the present invention is not limited to these examples. Product yield definitions in this patent specification:
the yield of DCPD DO reaction is 100% of the mol of DCPD DO in the reaction product/mol of DCPD raw material participating in the reaction.
Solvent distillation yield-the mass of solvent collected at the top of the column per hour/the mass of solvent entering the distillation column per hour-100%
The rectification yield of 2-phenyl-2-propanol (mass of 2-phenyl-2-propanol collected at the top of the column per hour/mass of 2-phenyl-2-propanol fed into the rectification column per hour) was 100%
The yield of DCPDO crystals is 100 percent of the mass of DCPDO obtained by crystal separation/the mass of DCPDO in the raw material of crystal separation
Example 1: preparation of titanium silicalite molecular sieve catalyst
Sequentially adding 10 g of hexadecylamine into 112ml of water and 110 ml of ethanol in a reactor under the conditions of room temperature and stirring, and stirring; adding 65 g of tetraethoxysilane and 0.12 g of ethyl titanate dissolved in 30 ml of ethanol into the solution, stirring for 30 minutes, crystallizing for 12 hours, adding 18.7 g of carbon nanofibers, continuously stirring for 10-72 hours, heating the reactor, crystallizing the reaction materials for 1 day at 200 ℃, filtering to obtain a solid, extracting the template agent in the catalyst by using ethanol, and then washing by using pure water until the eluent is neutral. And drying the washed solid at 110 ℃ for 12 hours to obtain the Ti-HMS taking the carbon nanofibers as the carrier.
Adding 3 times volume of pure water and 1.2 g of Mg (OH) into the Ti-HMS solid taking the carbon nanofibers as the carrier2Stirring for 48 hours at room temperature, separating out solids, washing with pure water until the water washing liquid is neutral, drying for 20 hours at 80 ℃, and then roasting for 20 hours at 400 ℃ in a helium atmosphere to obtain Ti-HMS modified by a magnesium-containing compound and taking carbon nanofibers as carriers;
tabletting and forming the prepared powder catalyst sample, crushing and screening, putting 50 g of 20-50-mesh particles into a reactor, adding 15.3 g of trimethylchlorosilane and 200 ml of toluene into the reactor, stirring, carrying out silanization at the reaction temperature of 120 ℃ for 10 hours, stopping the reaction, taking out the solid catalyst, washing the toluene, and drying for 30 hours in a vacuum system at the temperature of 80 ℃ and the system pressure of 0.133 KPa.
Examples 2 to 9: a kettle type reactor, and a mixed solution of DCPDO and 2-phenyl-2-propanol which are main products is obtained by catalytic oxidation:
feeding a titanium silicalite molecular sieve catalyst, cumene hydroperoxide CHP and a solvent into a 500 ml reaction kettle according to the process requirements, rectifying and separating the solvent and 2-phenyl-2-propanol after the reaction is finished, separating DCPDO, mixing a crystallization mother liquor and a fresh reaction raw material, feeding the mixture into the reactor, and continuing the reaction of the next batch. The influence of temperature, pressure, material ratio and reaction time on the yield of the DCPDO reaction product is considered, the composition of the catalyst used in the examples 2-9 is shown in a table 1, and the experimental result is shown in a table 2.
TABLE 1 composition of catalysts in percent by mass
Figure BDA0002726334550000071
Injecting: c-represents a carbon nanofiber.
TABLE 2 Process conditions for the batch Synthesis of DCPDO
Figure BDA0002726334550000081
Examples 10 to 17: mixed liquid of DCPDO and 2-phenyl-2-propanol synthesized by catalytic oxidation through fixed bed continuous reaction process
Taking 40 g of titanium silicalite molecular sieve catalyst, filling the titanium silicalite molecular sieve catalyst into a 100 ml isothermal fixed bed reactor, taking cumene hydroperoxide CHP as an oxidant, and pumping reaction liquid into the reactor through a metering pump. The solvent and the 2-phenyl-2-propanol are separated from the reaction product through rectification, the DCPDO is separated through crystallization, the crystallization mother liquor and the fresh reaction raw material are mixed and enter the reactor again, the influence of temperature, pressure, material ratio and space velocity on the yield of the DCPDO of the reaction product is inspected, the composition of the catalyst used in the examples 10-17 is shown in a table 3, and the experimental result is shown in a table 4.
TABLE 3 catalyst composition in percent by mass
Figure BDA0002726334550000082
Injecting: c-represents a carbon nanofiber.
TABLE 4 Process conditions for the fixed bed continuous reaction Synthesis of DCPDO
Figure BDA0002726334550000091
Examples 18 to 22: separating solvent, 2-phenyl-2-propanol, DCPDO by double-tower continuous rectification
The reaction products of examples 13, 14, 15, 16 and 17 were collected and subjected to a double-column continuous distillation separation operation, wherein the solvent was separated from the top of the first distillation column, 2-phenyl-2-propanol was separated from the top of the second distillation column, and DCPDDO and unreacted raw materials were collected from the bottom of the second distillation column. The solvent, the pressure at the top of the column, the temperature at the bottom of the column, the reflux ratio, the distillation yield of the solvent and the 2-phenyl-2-propanol in the material separated by distillation are shown in Table 5.
TABLE 5 Process conditions for the separation of solvent, 2-phenyl-2-propanol by two-column continuous rectification
Figure BDA0002726334550000092
Note: c9H12O represents 2-phenyl-2-propanol.
Examples 23 to 27: crystallization separation of solid DCPDO
The DCPDO sample after the solvent and 2-phenyl-2-propanol are separated by distillation in examples 18, 19, 20, 21 and 22 is added with fresh solvent to prepare DCPDDO hot saturated solution, the solution is cooled to a lower temperature, the solid DCPDO is separated by filtration by using the crystallization separation principle, and the mother liquor is mixed with fresh DCPD and CHP raw materials again and then enters a catalytic oxidation reactor for continuous reaction. The crystallization separation selection solvent, material ratio, temperature of the thermal saturated solution, material cooling temperature, and DCPDO crystallization yield are shown in Table 6.
TABLE 6 Process conditions for the crystallization separation of DCPDO
Figure BDA0002726334550000101
Example 28: the mother liquor of DCPD O separated by crystallization is used as reaction solvent, and the unreacted DCPD and the mono-oxidized dicyclopentadiene are recycled
835 g of the crystallization mother liquor of example 23 is taken and put into a 2L autoclave, and the crystallization mother liquor comprises the following components in percentage by mass: 0.2 percent of DCPD, 0.7 percent of dicyclopentadiene mono-oxide, 1.8 percent of DCPDO and 0.3 percent of 2-phenyl-2-propanol. Then, 40.8 g of 98% DCPD, 142.2 g of 83% CHP and 10 g of the catalyst used in example 4 are continuously added into the autoclave, the reaction system is replaced by nitrogen, the reaction temperature is controlled to be 80-85 ℃ and the pressure is 1MPa, the mixture is mechanically stirred and reacts for 4 hours, the feed liquid is cooled to room temperature, the composition of the product is analyzed, the mass fractions of the DCPD and the dicyclopentadiene monooxide are zero, the mass fraction of the DCPD DDO is 7.0%, and the reaction yield of the DCPDO is 100%. The reaction solution was rectified under reduced pressure to separate octane and 2-phenyl-2-propanol, and 76 g of crude DCPDO solid was obtained. Putting 76 g of crude DCPDDO and 800 g of octane recovered by rectification into a 1500 ml three-neck glass flask with a reflux condenser tube, heating the mixture in a water bath to 70 ℃ to obtain a DCPDDO saturated solution, cooling the solution to room temperature to separate out solid DCPDO, filtering and separating out the solid DCPDO, drying the solution at the system pressure of 500 Pa and the temperature of 80-90 ℃ for 4 hours, cooling the solution to the room temperature, weighing the solution to obtain 47.1 g of DCPDDO, and obtaining the crystallization separation yield of 94.5 percent (taking the fresh DCPD as the measurement standard).
While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the invention is not limited thereto, and that various changes and modifications may be made without departing from the spirit of the invention, and the scope of the appended claims is to be accorded the full scope of the invention.

Claims (10)

1. A process for preparing dicyclopentadiene dioxide, DCPDDO, and 2-phenyl-2-propanol, comprising:
(1) firstly, dicyclopentadiene DCPD is taken as a reaction raw material, cumene hydroperoxide CHP is taken as an oxidant, and the DCPD, the CHP and a titanium silicalite molecular sieve catalyst are fully contacted in an inert solvent to carry out catalytic oxidation reaction to generate main products (3, 4), (8, 9) -diepoxy-tricyclo [5,2,1,02,6]A mixture of decane DCPDO and 2-phenyl-2-propanol;
the titanium silicalite molecular sieve catalyst is a modified Ti-HMS molecular sieve catalyst with mesoporous characteristics, and comprises the following components: TiO 220.10-6.15 percent of mass fraction, 45.15-68.59 percent of mass fraction of nano carbon fiber and SiO2The mass fraction is 26.60-45.80%, the mass fraction of magnesium oxide is 0.01-2.00%, the mass fraction of silane group is 0.40-6.90%, and the UV-vis spectrogram of the catalyst has a strong absorption peak at 220 nm;
the catalytic oxidation reaction temperature is 30-150 ℃, the pressure is 0-10 MPa (gauge pressure), the molar ratio of CHP to DCPD is 1.8: 1-2.5: 1, the volume ratio of inert solvent to DCPD is 5: 1-30: 1;
(2) carrying out double-tower continuous rectification separation on the mixed liquor obtained in the step (1), collecting an inert solvent at the top of a first rectification tower, returning 50-80% of the solvent to a feed inlet of a catalytic oxidation reactor for recycling in the reactor, using 20-50% of the solvent for DCPDO crystallization separation, and conveying tower bottom liquid to a second rectification tower; collecting 2-phenyl-2-propanol from the top of the second rectifying tower, and collecting DCPDO and unreacted raw materials from the bottom of the second rectifying tower;
the first rectifying tower adopts reduced pressure rectification, the operating pressure of the tower top is 300-3000 Pa, the reflux ratio is 2: 1-10: 1, the temperature of the top of the tower is 20-60 ℃, the temperature of a tower kettle is 70-130 ℃, a solvent is collected at the top of the tower, and materials in the tower kettle are sent to a second rectifying tower;
and the second rectifying tower adopts reduced pressure rectification, the operating pressure at the top of the tower is 100-3000 Pa, and the reflux ratio is 2: 1-10: 1, the temperature of the top of the tower is 40-100 ℃, the temperature of the bottom of the tower is 60-155 ℃, the fraction collected at the top of the tower is 2-phenyl-2-propanol, and dicyclopentadiene dioxide and unreacted raw materials are collected at the bottom of the tower;
(3) adding an organic solvent into the DCPDO material collected in the tower kettle of the second rectifying tower in the step (2), and preparing a DCPDO saturated solution at the normal pressure and the temperature of 60-100 ℃, wherein the mass ratio of the DCPDO to the organic solvent is 1: 2-1: and 20, cooling the saturated solution to-5-30 ℃, separating out DCPDO solid in the solution, and separating to obtain solid DCPDO and crystallization mother liquor.
2. The method of claim 1, wherein: the catalytic oxidation reaction temperature in the step (1) is 60-140 ℃, the pressure is 0.3-3 MPa (gauge pressure), and the molar ratio of CHP to DCPD is 1.8: 1-2.2: 1.
3. The method of claim 1, wherein: the catalytic oxidation reaction in the step (1) adopts an intermittent reaction process or a fixed bed continuous reaction process; adopting an intermittent reaction process, wherein the mass ratio of the catalyst consumption to the DCPD is 0.01: 100-20: 100, the reaction time is 1-20 hours; a fixed bed continuous reaction process is adopted, and the total material volume airspeed is 0.1-4.2 h-1。
4. The method of claim 1, wherein: the mass ratio of the catalyst to the DCPD in the step (1) is 0.5: 100-15: 100, and the reaction time is 2-6 hours.
5. The method of claim 1, wherein: the inert solvent in the step (1) is any one selected from hexane, heptane, octane, nonane, decane, undecane, benzene, toluene, ethylbenzene, methyl ethylbenzene, xylene, cumene and petroleum ether.
6. The method of claim 1, wherein: in the step (2), the first rectifying tower adopts reduced pressure rectification, the operating pressure at the top of the tower is 600-2000 Pa, and the reflux ratio is 5: 1-8: 1, the tower top temperature is 25-46 ℃, and the tower kettle temperature is 80-130 ℃.
7. The method of claim 1, wherein: in the step (2), the second rectifying tower adopts reduced pressure rectification, the operating pressure at the top of the tower is 300-2000 Pa, and the reflux ratio is 5: 1-8: 1, the temperature of the top of the tower is 60-95 ℃, and the temperature of the bottom of the tower is 90-145 ℃.
8. The method of claim 1, wherein: the mass ratio of DCPDDO in the step (3) to the organic solvent is 1: 4-1: and 20, cooling the saturated solution to 20-30 ℃.
9. The method according to claim 1 or 8, characterized in that: the organic solvent is selected from any one of hexane, heptane, octane, nonane, decane, undecane, benzene, toluene, ethylbenzene, methyl ethylbenzene, xylene, cumene and petroleum ether.
10. The method of claim 1, wherein: the method further comprises the step (4):
(4) returning the crystallization mother liquor obtained in the step (3) to the catalytic oxidation reactor in the step (1), mixing with reaction raw materials DCPD, CHP and an inert solvent, and continuously reacting; or conveying the crystallized mother liquor to the first rectifying tower in the step (2) for rectifying and separating the solvent in the crystallized mother liquor.
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